WO2021145129A1 - Pilier conducteur et son procédé de fabrication, et procédé de fabrication de structure liée - Google Patents

Pilier conducteur et son procédé de fabrication, et procédé de fabrication de structure liée Download PDF

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Publication number
WO2021145129A1
WO2021145129A1 PCT/JP2020/047075 JP2020047075W WO2021145129A1 WO 2021145129 A1 WO2021145129 A1 WO 2021145129A1 JP 2020047075 W JP2020047075 W JP 2020047075W WO 2021145129 A1 WO2021145129 A1 WO 2021145129A1
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WIPO (PCT)
Prior art keywords
copper fine
base material
conductive pillar
thin film
fine particle
Prior art date
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PCT/JP2020/047075
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English (en)
Japanese (ja)
Inventor
亮太 山口
真 矢田
Original Assignee
Dic株式会社
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Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to US17/791,652 priority Critical patent/US20230041521A1/en
Priority to JP2021549079A priority patent/JP7107448B2/ja
Priority to KR1020227023782A priority patent/KR20220128352A/ko
Publication of WO2021145129A1 publication Critical patent/WO2021145129A1/fr

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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/16227—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation the bump connector connecting to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/818—Bonding techniques
    • H01L2224/81801—Soldering or alloying
    • H01L2224/81815—Reflow soldering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L24/14—Structure, shape, material or disposition of the bump connectors prior to the connecting process of a plurality of bump connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L24/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector

Definitions

  • the present invention relates to a conductive pillar, a method for manufacturing the same, and a method for manufacturing a bonded structure.
  • a flip chip mounting method has been used as a method of electrically connecting a semiconductor chip and a semiconductor substrate.
  • the flip chip mounting method is a method in which bumps are formed on an electrode pad arranged on a semiconductor chip, the semiconductor chip and the semiconductor substrate are placed facing each other via the bumps, and the bumps are melted and joined by heating.
  • a conductive pillar may be formed on an electrode pad arranged on a semiconductor chip via a plating base layer called a seed layer, and a bump may be formed on the conductive pillar.
  • the copper pillar is conventionally formed by the method shown below.
  • a plating base layer and a resist layer are formed in this order on a semiconductor chip having an electrode pad.
  • a part of the resist layer is removed to expose the plating base layer on the electrode pad.
  • a copper pillar is formed on the plating base layer by using an electroplating method.
  • the resist layer is removed, and the plating base layer arranged under the resist layer is removed by etching (see, for example, Patent Document 1).
  • Patent Document 2 A method of forming copper pillars using copper paste as a raw material without using an electroplating method has also been reported (see, for example, Patent Document 2).
  • the equipment introduction cost for adopting the electroplating method is high, and it is necessary to regenerate or dispose of a large amount of waste liquid, which also has a large environmental load.
  • the electrode on the base material on the semiconductor chip side may use aluminum or a metal type mainly composed of aluminum as the metal material. It is common. Aluminum is very easily oxidized and an oxide film is formed instantly. As a result, it is difficult to bond the copper paste under non-pressurized conditions because the oxide film inhibits the bonding with copper.
  • the present invention has been made in view of the above circumstances, and is a conductive pillar provided on a base material such as a semiconductor chip and capable of joining the base material and a member to be joined with high bonding strength via a bonding layer. And its manufacturing method. Another object of the present invention is to provide a method for manufacturing a bonding structure and a method for manufacturing an electronic device, which have the conductive pillars of the present invention and can bond a base material and a member to be bonded with high bonding strength.
  • a method for producing a conductive pillar including an electrode pad, a first bonding layer made of a Cu thin film on the electrode pad, and a sintered body of copper fine particles on the first bonding layer.
  • the step of sintering the copper fine particle paste further comprising a step of removing the residue of the copper fine particle paste remaining on the surface of the outermost layer on the base material, according to the above [1] or [2].
  • the method for manufacturing a conductive pillar according to the description.
  • a conductive pillar of the present invention it is possible to manufacture a conductive pillar capable of joining a base material and a member to be joined with high bonding strength via a bonding layer without using an electroplating method.
  • a bonded structure capable of bonding a base material and a member to be bonded with a high bonding strength via a bonding layer can be produced without using an electroplating method, and the bonding structure is included.
  • FIG. 1 (A) to 1 (D) are process diagrams for explaining an example of the method for manufacturing the conductive pillar of the present embodiment.
  • FIG. 2 is a cross-sectional view showing an example of the conductive pillars obtained by the method for manufacturing the conductive pillars of the present embodiment.
  • 3 (A) to 1 (D) are process diagrams for explaining an example of the method for manufacturing the conductive pillar of the present embodiment.
  • FIG. 4 is a cross-sectional view showing an example of the conductive pillars obtained by the method for manufacturing the conductive pillars of the present embodiment.
  • FIG. 5 is a cross-sectional view showing an example of the conductive pillars obtained by the method for manufacturing the conductive pillars of the present embodiment.
  • FIG. 6 (A) to 6 (C) are process diagrams for explaining an example of a method for manufacturing the bonded structure of the present embodiment.
  • FIG. 7A is a cross-sectional view showing an example of the joint structure obtained by the method for manufacturing the joint structure of the present embodiment.
  • FIG. 7B is a cross-sectional view showing another example of the joint structure obtained by the method for manufacturing the joint structure of the present embodiment.
  • 8 (A) to 8 (C) are process diagrams for explaining an example of a method for manufacturing the bonded structure of the present embodiment.
  • FIG. 9A is a cross-sectional view showing an example of the joint structure obtained by the method for manufacturing the joint structure of the present embodiment.
  • FIG. 9B is a cross-sectional view showing another example of the joint structure obtained by the method for manufacturing the joint structure of the present embodiment.
  • FIG. 10 is a graph showing the particle size distribution of the copper fine particles.
  • FIG. 11 is a photomicrograph of a cross section of the conductive pillar of Example 1.
  • FIG. 12 is a photomicrograph of the upper surface of the conductive pillar of Example 1.
  • the conductive pillar, the bonding structure, the electronic device, and the method for manufacturing the conductive pillar of the present invention will be described in detail with reference to the drawings.
  • the feature portion may be enlarged and shown for convenience. Therefore, the dimensional ratio of each component may differ from the actual one.
  • 1 and 3 are process diagrams for explaining an example of a method for manufacturing a conductive pillar.
  • the method for manufacturing the conductive pillars shown in FIG. 1 is defined as the first embodiment
  • the method for manufacturing the conductive pillars shown in FIG. 3 is defined as the second embodiment
  • the method for manufacturing the conductive pillars according to the present invention is described below. This will be described in detail.
  • FIG. 1 is a diagram showing an example of a method for manufacturing a conductive pillar according to the present embodiment.
  • the method for manufacturing a conductive pillar of the present embodiment is a conductive body including an electrode pad, a first bonding layer made of a Cu thin film on the electrode pad, and a sintered body of copper fine particles on the first bonding layer. It is a method of manufacturing sex pillars.
  • a step of forming a Cu thin film by sputtering or depositing Cu on the surface of a base material on which an electrode pad is formed (FIG. 1 (A)).
  • a step of forming a resist layer having an opening on the electrode pad on the Cu thin film (FIG. 1 (B)).
  • the step of filling the opening with the copper fine particle paste (FIG. 1 (C)) and A step of heating the base material filled with the copper fine particle paste and sintering the copper fine particle paste (FIG. 1 (D)). Are prepared in this order.
  • FIG. 3 is a side view showing an example of the method for manufacturing the conductive pillar of the present embodiment.
  • the method for manufacturing the conductive pillar of the present embodiment includes a step of forming a resist layer having an opening on the electrode pad on a base material on which the electrode pad is formed (FIG. 3 (A)).
  • a step of sputtering or vapor-depositing Cu on the surface of the base material on which the resist layer having the openings is formed to form a Cu thin film (FIG. 3 (B)).
  • the step of filling the opening with the copper fine particle paste (FIG. 3 (C))
  • a step of heating the base material filled with the copper fine particle paste and sintering the copper fine particle paste (FIG. 3 (D)).
  • Step of forming a Cu thin film In the step of forming the Cu thin film in the first embodiment, Cu is sputtered or vapor-deposited on the surface of the base material on which the electrode pad 13 is formed to form the Cu thin film 17 (see FIG. 1 (A)). In the present embodiment, since the electrode pad 13 is formed on the base material 11, as shown in FIG. 1A, not only the surface on which the base material 11 is exposed but also the electrode pad on the base material 11 is formed. A Cu thin film 17 is also formed on the surface above 13.
  • Cu is sputtered or vapor-deposited on the surface of the base material on which the resist layer 16 having the opening 16a is formed to form the Cu thin film 17 (see FIG. 3B). ).
  • the resist layer 16 since the resist layer 16 has an opening 16a on the electrode pad 13, as shown in FIG. 3B, not only on the surface of the resist layer 16 but also on the base material 11 exposed by the opening 16a.
  • a Cu thin film 17 is also formed on the surface of the electrode pad 13.
  • the film thickness of the Cu thin film 17a on the upper part of the resist layer is substantially equal to the film thickness of the Cu thin film 17c on the electrode pad.
  • the film thickness of the Cu thin film 17b on the side surface of the opening of the resist layer is thinner than the film thickness of the Cu thin film 17a on the upper part of the resist layer and the film thickness of the Cu thin film 17c on the electrode pad.
  • the film thickness of the Cu thin film 17b on the side surface of the opening of the resist layer is the film thickness of the Cu thin film 17a on the upper part of the resist layer and the Cu thin film on the electrode pad when the substrate is tilted and rotated during sputtering. It can be made substantially equal to the film thickness of 17c.
  • the base material 11 having the electrode pad 13 is not particularly limited, and examples thereof include semiconductor material base materials such as semiconductor chips, semiconductor wafers, and interposers on which an arbitrary electric circuit is formed.
  • semiconductor material base materials such as semiconductor chips, semiconductor wafers, and interposers on which an arbitrary electric circuit is formed.
  • known materials used for the base material 11 such as metals such as copper, ceramics, silicon, resins, and composite materials thereof, can be used.
  • a conductive material made of a metal or alloy such as Ti, Cu, Al, Au can be used.
  • the electrode pad 13 may have a single-layer structure made of one kind of material, or may have a multi-layer structure made of two or more kinds of materials.
  • the outermost layer of the electrode pad 13 in contact with the Cu thin film is preferably a titanium-containing layer because the wettability with the Cu thin film, that is, the adhesion is improved and stable conductive pillars can be formed.
  • TiW / Cu titanium-titanium alloy / copper
  • Ti / Cu titanium / copper
  • Ti / NiAu titanium / copper / nickel gold
  • titanium / titanium nitride titanium nitride.
  • a multi-layer structure such as titanium (Ti / TiN / Ti) can be mentioned.
  • the Cu thin film 17 is formed by sputtering Cu on a surface on a substrate on which an electrode pad is formed or on a surface on the substrate on which a resist layer having an opening is formed, using a commercially available sputtering apparatus. be able to. Specifically, an inert gas such as Ar is introduced in a vacuum, a negative voltage is applied to the Cu target to generate a glow discharge, the inert gas atom is ionized, and gas ions are generated on the surface of the target at high speed.
  • an inert gas such as Ar is introduced in a vacuum, a negative voltage is applied to the Cu target to generate a glow discharge, the inert gas atom is ionized, and gas ions are generated on the surface of the target at high speed.
  • the Cu atom of the Cu target is violently ejected by colliding with each other and violently ejected, and adheres and deposits on the surface on the base material on which the electrode pad is formed or on the surface on the base material on which the resist layer having an opening is formed. To form a Cu thin film.
  • Cu is vapor-deposited on the surface of the base material on which the electrode pad is formed or on the surface of the base material on which the resist layer having an opening is formed to form a Cu thin film.
  • a Cu vapor deposition material is placed on a heat generating source (vapor deposition source) inside the vacuum vapor deposition apparatus and heat is applied in a vacuum, the heated Cu vapor deposition material is vaporized and sublimated, and the inside of the vacuum vapor deposition apparatus is inside.
  • Cu atoms scattered in the vacuum of the above adhere (evaporate) to the surface on the base material on which the electrode pad is formed or the surface on the base material on which the resist layer having an opening is formed to form a Cu thin film. do.
  • the film thickness of the Cu thin film 17 can be easily adjusted in the range of 3 to 3000 nm, preferably 3 to 3000 nm, more preferably 10 to 2000 nm, and particularly preferably 50 to 1000 nm. ..
  • the Cu thin film 17 may have a single-layer structure, or may have a multi-layer structure formed of two or more kinds of materials as long as the Cu thin film can be formed on the outermost layer.
  • the electrode pad 13 is made of an easily oxidizable metal such as aluminum
  • the bonding strength between the electrode pad 13 and the conductive pillar 1 is easily increased. In order to do so, it is necessary to prevent the oxide film from being formed on the electrode pad 13 or to remove the oxide film. Rather than forming a Cu thin film directly on the aluminum electrode pad 13, it is better to form a Ti thin film on the aluminum electrode pad 13 and to form a Cu thin film on the Ti thin film. In some cases, the bonding strength between the and the conductive pillar 1 can be easily increased.
  • the formation of the Ti thin film can be formed by sputtering or vapor deposition of Ti in the same manner as the formation of the Cu thin film, except that the Cu target in the formation of the Cu thin film is changed to the Ti target.
  • the film thickness of the Ti thin film can be easily adjusted in the range of 3 to 600 nm, preferably 3 to 600 nm, more preferably 10 to 400 nm, and particularly preferably 50 to 200 nm.
  • the Cu thin film functions as a first bonding layer between the electrode pad and the copper pillar, and it is not necessary to pass a current as in the electroplating method. , The film thickness of the Cu thin film can be reduced.
  • the film thickness of the Cu thin film can be reduced, there is an advantage that the time for removing the Cu thin film by etching can be significantly shortened and the amount of the etching agent used can be reduced.
  • the resist is formed in the method for producing conductive pillars of the second embodiment. In the process of removing the layer, it is possible to prevent the occurrence of undercut, which has been a conventional problem. Even if the electrode pad 13 has a multi-layer structure formed of, for example, two or more kinds of metal materials such as Ti and Al, the occurrence of undercut can be prevented.
  • the resist layer can remove a part of the resist layer 16 to form an opening 16a formed of a columnar recess that exposes the electrode pad 13 (FIG. 1 (B). ), See FIG. 3 (A)).
  • a patterning method for the resist layer 16 a known method can be used.
  • the opening 16a functions as a mold for manufacturing the sintered body 12.
  • the resist layer 16 in FIG. 1B may have a shape having an opening 16a on the electrode pad 13 on the Cu thin film 17.
  • the resist layer 16 in FIG. 3A can have a shape having an opening 16a on the electrode pad 13 on the base material 11.
  • various dry films such as photoresist (photo-resist), polyimide, epoxy, and epoxy molding compound (EMC) can be used.
  • the opening 16a has a substantially cylindrical shape.
  • the bondability between the sintered body 12 and the first bonding layer and the bonding layer (second bonding layer) described later becomes good, and the substrate 11 and the substrate 11 , The base material 11 and the member to be bonded are bonded with higher bonding strength, which is preferable.
  • the size of the opening 16a and the size of the conductive pillar 1 that can be formed by the opening 16a can be represented by the diameter of the bottom surface of the cylinder, and the joining accompanying the miniaturization of the electronic device
  • the diameter is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and particularly preferably 30 ⁇ m or less so that the structure can be miniaturized.
  • the size of the opening 16a and the size of the conductive pillar 1 are 5 ⁇ m or more in diameter because the bondability and conductivity with the first bonding layer and the second bonding layer described later are further improved. It is preferably 10 ⁇ m or more, and more preferably 20 ⁇ m or more.
  • the diameter of the bottom surface of the cylinder is preferably 5 to 100 ⁇ m, more preferably 10 to 50 ⁇ m, and even more preferably 20 to 30 ⁇ m.
  • the planar shape of the opening 16a is not limited to a substantially circular shape, and can be appropriately determined according to the planar shape of the electrode pad 13.
  • the planar shape of the opening 16a may be, for example, a polygonal shape such as a substantially rectangular shape, or a shape such as a substantially elliptical shape or a substantially oval shape.
  • the size of the opening 16a and the size of the conductive pillar 1 that can be formed by the opening 16a can be represented by the equivalent circle diameter of the planar shape, and the preferable circle equivalent diameter is the diameter of the bottom surface of the cylinder. Is similar to.
  • the planar shape of the sintered body 12 can be formed into a polygonal shape such as a substantially rectangular shape, a substantially elliptical shape, a substantially oval shape, or the like, and the size of the sintered body 12 can be controlled. be able to.
  • the size of the opening 16a and the size of the conductive pillar 1 that can be formed by the opening 16a can be represented by the diameter equivalent to the circle on the bottom surface of the pillar shape, and the size of the electronic device is small.
  • the equivalent circle diameter is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and particularly preferably 30 ⁇ m or less so that the joint structure can be miniaturized due to the change.
  • the size of the opening 16a and the size of the conductive pillar 1 have a diameter equivalent to the circle because the bondability and conductivity with the first bonding layer and the second bonding layer described later are further improved.
  • Is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 20 ⁇ m or more.
  • the equivalent circle diameter is preferably 5 to 100 ⁇ m, more preferably 10 to 50 ⁇ m, and even more preferably 20 to 30 ⁇ m.
  • the opening 16a with the copper fine particle paste 12c When filling the opening 16a with the copper fine particle paste 12c, it may be carried out in an inert gas atmosphere such as an argon gas atmosphere or in a reducing gas atmosphere. In this case, the copper fine particles contained in the copper fine particle paste 12c are less likely to be oxidized, which is preferable.
  • the squeegee 12d used for filling the copper fine particle paste 12c for example, one made of rubber such as plastic or urethane rubber, ceramic, or metal can be used.
  • the method of filling the opening 16a with the copper fine particle paste 12c is not limited to the method using the squeegee 12d, but a method such as a doctor blade, a dispenser, an inkjet, press injection, vacuum printing, or pressing by pressure is used. You may. Next, (copper fine particle paste) that can be used in ⁇ step of filling copper fine particle paste> will be described.
  • the copper fine particle paste 12c to be filled in the opening 16a it is preferable to use one containing copper fine particles having an average primary particle diameter of less than 1 ⁇ m.
  • the copper fine particle paste 12c for example, a mixture of copper fine particles having an average primary particle diameter of less than 1 ⁇ m, a solvent, and a dispersant, a protective agent, and other additives contained as necessary can be used.
  • the copper fine particles and the dispersant may be contained in the copper fine particle paste 12c as a composite of the copper fine particles and the dispersant.
  • the copper fine particles and the protective agent may be contained in the copper fine particle paste 12c as a complex of the copper fine particles and the protective agent.
  • the copper fine particle paste 12c can be produced, for example, by mixing a material to be a copper fine particle paste 12c by a known method.
  • the complex of copper fine particles and a dispersant and the composite of copper fine particles and a protective agent are collectively referred to as "copper fine particle complex”.
  • the average primary particle size of the copper fine particles and the average primary particle size of the copper fine particle composite are preferably less than 1 ⁇ m, more preferably 500 nm or less, still more preferably 100 nm or less.
  • the average primary particle size of the copper fine particles and the average primary particle size of the copper fine particle composite are preferably 10 nm or more and less than 1 ⁇ m, more preferably 20 nm or more and 500 nm or less, and further preferably 30 nm or more and 100 nm or less.
  • the shape of the copper fine particles contained in the copper fine particle paste 12c There is no particular limitation on the shape of the copper fine particles contained in the copper fine particle paste 12c.
  • the copper fine particles spherical or flake-shaped copper fine particles can be used.
  • the average primary particle diameter of the copper fine particles used as the material of the conductive pillar 1 is a small-angle X-ray scattering measurement method for the copper fine particles forming the sintered body 12 (conductive pillar 1) after sintering. (Hereinafter, it may be referred to as "SAXS"), and the average particle size is appropriately determined so as to be within a predetermined range.
  • SAXS small-angle X-ray scattering measurement method for the copper fine particles forming the sintered body 12 (conductive pillar 1) after sintering.
  • SAXS small-angle X-ray scattering measurement method for the copper fine particles forming the sintered body 12 (conductive pillar 1) after sintering.
  • SAXS small-angle X-ray scattering measurement method for the copper fine particles forming the sintered body 12 (conductive pillar 1) after sintering.
  • the average primary particle size of the copper fine particles contained in the copper fine particle paste 12c is 100 nm. It is as follows.
  • the particle size of the copper fine particles used as the material of the conductive pillar 1 is less than 1 ⁇ m, which means that the average primary particle size of the copper fine particles is less than 1 ⁇ m.
  • the average primary particle size of the composite is copper. It is regarded as the average primary particle size of fine particles.
  • the average primary particle size of the copper fine particles used as the material of the conductive pillar 1 can be calculated by observation with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • a value calculated by analyzing an image of a photograph taken with a transmission electron microscope (TEM) is used as the average primary particle diameter of the copper fine particles used as the material of the conductive pillar 1.
  • a dispersion liquid in which copper fine particles are dispersed in a solvent at an arbitrary concentration is cast on a carbon film-coated grid and dried to remove the solvent, and a sample for observation with a transmission electron microscope (TEM). And. 200 fine particles are randomly extracted from the obtained TEM image. The area of each of the extracted fine particles is obtained, and the value calculated based on the number of particles when converted into a true sphere is adopted as the average primary particle diameter. Randomly sampled copper particles are excluded from overlapping two particles. When a large number of particles are aggregated by contact or secondary aggregation, the copper fine particles constituting the aggregate are treated as independent particles. For example, when five primary particles are contacted or secondarily aggregated to form one aggregate, each of the five particles constituting the aggregate is a target for calculating the average primary particle size of the copper fine particles.
  • the copper fine particles contained in the copper fine particle paste 12c (the copper fine particles are a composite with the dispersant and the composite with the dispersant) so that the copper fine particle paste 12c in which the copper fine particles are uniformly dispersed can be obtained. / Or, in the case of a complex with a protective agent, it is preferable to use one that does not aggregate the complex).
  • the solvent one or more kinds of solvents containing hydroxyl groups may be used, one or more kinds of solvents not containing hydroxyl groups may be used, or a solvent containing hydroxyl groups and a solvent not containing hydroxyl groups are mixed. May be used.
  • Examples of the solvent containing a hydroxyl group include water, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, sec-butanol, tert-butanol, amyl alcohol, tert-amyl alcohol, 1-hexanol, and cyclohexanol.
  • Benzyl alcohol 2-ethyl-1-butanol, 1-heptanol, 1-octanol, 4-methyl-2-pentanol, neopentyl glycol, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4- Butanediol, 2,3-butanediol, isobutylene glycol, 2,2-dimethyl-1,3-butanediol, 2-methyl-1,3-pentanediol, 2-methyl-2,4-pentanediol, diethylene glycol, Triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 2,4-pentanediol, dipropylene glycol, 2,5-hexanediol, glycerin, diethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether ,
  • solvent containing no hydroxyl group examples include acetone, cyclopentanone, cyclohexanone, acetamide, acrylonitrile, propionitrile, n-butyronitrile, isobutyronitrile, ⁇ -butyrolactone, ⁇ -caprolacto, propiolactone, and carbon dioxide-2.
  • Examples of the additive contained in the copper fine particle paste 12c include a silicon-based leveling agent, a fluorine-based leveling agent, and a defoaming agent.
  • a thioether type organic compound or the like can be used as the dispersant contained in the copper fine particle paste 12c.
  • the thioether-type organic compound suitable as a dispersant include ethyl 3- (3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanyl) propionate represented by the following formula (1) [polyethylene glycol methylglycidyl ether (polyethylene glycol methylglycidyl ether (1)). Addition compound of ethyl 3-mercaptopropionate to polyethylene glycol chain having a molecular weight of 200 to 3000 (8 to 136 carbon atoms)] and the like.
  • Me represents a methyl group
  • Et represents an ethyl group
  • N is 200 to 3000.
  • the compound represented by the formula (1) is an addition compound of ethyl 3-mercaptopropionate to polyethylene glycol methyl glycidyl ether, and the molecular weight of the polyethylene glycol chain in polyethylene glycol methyl glycidyl ether is 200 to 3000 (8 to 136 carbon atoms). )belongs to.
  • the polyethylene glycol chain has a molecular weight of 200 (8 carbon atoms), 1000 (46 carbon atoms), 2000 (91 carbon atoms), 3000 (136 carbon atoms).
  • the copper fine particles can be satisfactorily dispersed in the solvent, and aggregation due to poor dispersion can be suppressed. Further, when the molecular weight is 3000 or less, the dispersant is less likely to remain in the sintered body 12 formed by sintering the copper fine particle paste 12c.
  • the wettability of the sintered body 12 with respect to the material to be the second bonding layer, which will be described later, is improved, and the material to be the second bonding layer is easily filled in the plurality of groove portions 12a of the sintered body 12, and an anchor portion is formed. It becomes easy to be done.
  • the compound represented by the formula (1) forms a complex with the copper fine particles.
  • the complex of the compound represented by the formula (1) and the copper fine particles is easily and uniformly dispersed in a solvent such as water and ethylene glycol. Therefore, by using the complex of the compound represented by the formula (1) and the copper fine particles, the copper fine particle paste 12c in which the copper fine particles are uniformly dispersed can be easily obtained.
  • the copper fine particle paste 12c in which the copper fine particles are uniformly dispersed By using the copper fine particle paste 12c in which the copper fine particles are uniformly dispersed, a conductive pillar 1 having stable characteristics in which the copper fine particles are uniformly arranged can be obtained.
  • the composite of the copper fine particles and the dispersant can be produced, for example, by a method of mixing and reacting the copper fine particles and the dispersant.
  • Examples of the complex of the copper fine particles and the dispersant include a complex [1] and a complex [2] produced by the methods shown below.
  • the complex [1] and the complex [2] may be purified as necessary and then used as a material for the copper fine particle paste 12c.
  • the copper fine particle paste 12c is filled in the opening 16a to form a columnar body, at least the surface of the columnar body (FIG. It is preferable to perform a step of exposing 1 (C) and the upper surface in FIG. 3 (C) to an oxygen-containing atmosphere having an oxygen concentration of 200 ppm or more. As a result, the copper fine particles contained in the copper fine particle paste 12c forming the surface of the columnar body are oxidized.
  • the oxygen concentration in the oxygen-containing atmosphere that exposes at least the surface of the columnar body is preferably 200 ppm or more, and more preferably 1000 ppm or more.
  • the oxygen concentration in the oxygen-containing atmosphere that exposes at least the surface of the columnar body is preferably 30% or less, more preferably 25% or less, and the oxygen concentration in the atmosphere (20.1%) or less. Is even more preferable.
  • the oxygen concentration in the oxygen-containing atmosphere is 30% or less, it is possible to prevent the copper fine particles contained in the copper fine particle paste 12c forming the columnar body from being excessively oxidized.
  • the exposure time for exposing at least the surface of the columnar body to an oxygen-containing atmosphere having an oxygen concentration of 200 ppm or more can be appropriately determined depending on the exposure temperature, the type of copper fine particles contained in the copper fine particle paste 12c, and the like.
  • the exposure time is not particularly limited, but for example, when exposed to an oxygen-containing atmosphere having an oxygen concentration of 200 ppm or more in an environment of a temperature of 25 ° C., it is preferably in the range of 1 minute to 180 minutes, and in the range of 3 minutes to 60 minutes. Is more preferable.
  • the exposure time is 1 minute or more, the copper fine particles contained in the copper fine particle paste 12c forming the surface of the columnar body are sufficiently oxidized.
  • the conductivity of the sintered body 12 obtained after sintering may become insufficient. There is.
  • the sintered body 12 may be reduced by a conventionally known method, if necessary, after forming the sintered body 12. Examples of the oxygen-containing atmosphere having an oxygen concentration of 200 ppm or more include the atmosphere.
  • the columnar body (copper fine particle paste 12c) maintains a state of being firmly adhered to the inner surface of the opening 16a of the resist layer 16, and the bottom of the opening 16a before and after sintering. Since the portion in close contact with the Cu thin film 17 is prevented from shrinking in the direction parallel to the surface of the base material, the planar shape of the sintered body does not change from the planar shape of the columnar body.
  • the columnar body (copper fine particle paste 12c) and the Cu thin film covering the side surface thereof maintain a state of being firmly adhered to the inner surface of the opening 16a of the resist layer 16 before and after sintering. Since the shrinkage is inhibited in the direction parallel to the surface of the base material exposed to the opening 16a, the planar shape of the sintered body does not change from the planar shape of the columnar body.
  • the conductive pillars obtained through the step of sintering the copper fine particle paste are excellent in dimensional stability. Since the sintered body 12 of the copper fine particles is formed directly on the first bonding layer 17c made of the Cu thin film on the electrode pad 13, the space between the first bonding layer 17c and the sintered body 12 is strong. Can be combined with. In the conductive pillar 1, since the first bonding layer 17c made of the Cu thin film 17 and the sintered body 12 are firmly bonded to each other, it is presumed that the strength of the conductive pillar 1 is improved.
  • the conductive pillar 1 is composed of an electrode pad 13 on the base material 11, a Cu thin film (first bonding layer 17c) on the electrode pad 13, and a sintered body 12 on the first bonding layer 17c. There is. Since the sintered body 12 has a porous structure, it can be distinguished from the Cu thin film 17. Further, since the sintered body 12 has a porous structure, it is considered that the sintered body 12 plays a role as a stress relaxation layer in the conductive pillar and contributes to the improvement of the bonding strength.
  • the exposed surface (upper surface in FIGS. 1C and 3C) of the columnar body Prior to the step of forming the sintered body 12, at least the exposed surface (upper surface in FIGS. 1C and 3C) of the columnar body is exposed to an oxygen-containing atmosphere having an oxygen concentration of 200 ppm or more.
  • the upper surface 12b of the sintered body 12 extends from the upper surface 12b toward the base material 11 as shown in FIGS. 1D and 3D.
  • a plurality of groove portions 12a are formed. It is presumed that this is because the copper fine particles contained in the copper fine particle paste 12c forming the surface of the columnar body to be the sintered body 12 are oxidized.
  • the paste containing metal fine particles is applied onto the base material.
  • a series of steps from the step to the completion of sintering are performed in an inert gas atmosphere. This is to prevent the metal fine particles such as copper fine particles contained in the paste containing the metal fine particles from being oxidized (see, for example, Japanese Patent No. 6168837 and Japanese Patent No. 6316683). Therefore, in the conventional technique, the atmosphere is not changed in the middle of a series of steps from the step of applying the paste containing the metal fine particles on the base material to the completion of sintering, and the metal applied on the base material is not changed.
  • the paste containing the fine particles was not exposed to an oxygen-containing atmosphere before being sintered, and no groove was formed on the upper surface of the sintered body.
  • the step of removing the copper fine particle paste 12c remaining on the upper part of the resist layer, or the copper fine particle paste 12c remaining on the Cu thin film 17a on the upper part of the resist layer may be added.
  • a step of removing the copper fine particle paste 12c a method of wiping with a cloth may be used, but in order to remove all the copper fine particle paste 12c on the upper part of the resist layer, it is preferable to adopt an etching method of washing away with a cleaning liquid.
  • FIG. 2 in the step of removing the residue of the copper fine particle paste remaining on the surface of the outermost layer on the base material after the step of sintering the copper fine particle paste, FIG. As shown in FIG. 2, the Cu thin film 17a on the upper part of the resist layer shown in D) can be removed at the same time. Therefore, the copper fine particle paste remaining on the Cu thin film 17a on the upper part of the resist layer before the step of sintering the copper fine particle paste.
  • the step of removing 12c can be omitted, and there is an advantage that the number of steps and the manufacturing cost can be reduced.
  • tentative firing may be performed in which the solvent contained in the columnar body is volatilized at a low temperature before firing the columnar body.
  • the firing method for firing the columnar body is not particularly limited, and for example, a vacuum solder reflow device, a hot plate, a hot air oven, or the like can be used.
  • the copper fine particles contained in the columnar body are fused to each other, and the sintered body 12 having sufficient conductivity and strength is obtained. Any range is sufficient as long as it can be obtained.
  • the temperature for heating the base material filled with the copper fine particle paste is preferably 150 to 350 ° C, more preferably 200 to 250 ° C.
  • the heating time is preferably in the range of 1 to 60 minutes, more preferably in the range of 5 to 15 minutes.
  • the temperature at which the copper fine particles are fused can be measured using a thermogravimetric analyzer (TG-DTA) or a differential scanning calorimeter (DSC).
  • TG-DTA thermogravimetric analyzer
  • DSC differential scanning calorimeter
  • the atmosphere at the time of sintering is not particularly limited, but from the viewpoint of preventing the oxidation of copper particles, it is preferable to fire in an atmosphere of an inert gas such as nitrogen or argon, and a reducing gas is used. May be good.
  • a copper fine particle paste 12c having an average primary particle size of less than 1 ⁇ m is used to produce a sintered body 12 of copper fine particles having an average particle size of less than 1 ⁇ m measured using SAXS.
  • the copper fine particle paste 12c having an average primary particle diameter of less than 1 ⁇ m of the copper fine particles has good filling property when filled in the opening 16a. Therefore, the conductive pillar 1 made of the sintered body 12 formed by sintering the copper fine particle paste 12c (columnar body) filled in the opening 16a has good conductivity containing copper fine particles at a high density. Become.
  • the copper fine particle paste 12c has good filling property, it is possible to form a fine conductive pillar 1 that can cope with the miniaturization of the bonded structure. Moreover, since the copper fine particle paste 12c has good filling property, the sintered body 12 formed by sintering the copper fine particle paste 12c (columnar body) is a Cu thin film 17 (first bonding) on the electrode pad 13. The bondability and electrical connection with the layer 17c) and the second bonding layer described later are improved.
  • the copper fine particle paste 12c contains copper fine particles having an average primary particle diameter of 100 nm or less.
  • the copper fine particle paste 12c has even better filling properties when it is filled in the opening 16a, which is more preferable. Specifically, when the average primary particle diameter of the copper fine particles contained in the copper fine particle paste 12c is 100 nm or less, for example, even if the opening 16a is a fine particle having a cylindrical shape with a diameter of 100 ⁇ m, the conductive paste 12c Can be filled in the opening 16a at a high density.
  • the average particle size of the conductive pillar 1 measured using SAXS is preferably less than 1 ⁇ m, more preferably 500 nm or less, still more preferably 100 nm or less.
  • the average particle size of the conductive pillar 1 measured using SAXS is preferably 10 nm or more and less than 1 ⁇ m, more preferably 20 nm or more and 500 nm or less, and further preferably 30 nm or more and 100 nm or less.
  • the copper fine particles obtained by sintering the copper fine particle paste 12c (columnar body) are obtained.
  • the shape of the conductive pillar 1 can be formed by the fusion function between the particles.
  • the sintered body 12 to be the conductive pillar 1 is placed on the electrode pad 13 on the base material 11 having the electrode pad 13 via a Cu thin film (that is, the first bonding layer 17c). (See FIGS. 1 (D) and 3 (D)).
  • the electrode pad 13 is often made of aluminum. If an oxide film is formed on the surface of the aluminum electrode pad 13, the bonding strength (share strength) between the electrode pad 13 and the sintered body 12 may be impaired, but the conductive pillar of the present embodiment In the manufacturing method of 1, since the Cu thin film (that is, the first bonding layer 17c) is formed on the surface above the electrode pad 13, it is possible to prevent the oxide film from being formed on the surface of the electrode pad 13. As a result, the electrode pad 13 made of aluminum and the conductive pillar 1 made of the sintered body 12 can be bonded with high bonding strength (share strength).
  • the sintered body 12 Since the opening 16a has a substantially cylindrical shape, the sintered body 12 has a substantially cylindrical outer shape. When the sintered body 12 has a substantially columnar outer shape, the bondability with the second bonding layer described later becomes good, and the base material 11 and the member to be joined to be bonded to the base material 11 Is preferable because it is bonded with a higher bonding strength.
  • the size of the substantially cylindrical sintered body 12 is preferably 200 ⁇ m or less in diameter, more preferably 100 ⁇ m or less, and particularly preferably 100 ⁇ m or less so as to be able to cope with the miniaturization of the joint structure accompanying the miniaturization of electronic devices. Is 50 ⁇ m or less.
  • the size of the sintered body 12 is preferably 5 ⁇ m or more in diameter, and more preferably 10 ⁇ m or more, because the bondability and conductivity with the second bonding layer, which will be described later, will be further improved. , 20 ⁇ m or more is more preferable.
  • the diameters of the upper surface and the bottom surface of the substantially cylindrical sintered body 12 are preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m, and even more preferably 20 to 50 ⁇ m.
  • the planar shape of the sintered body 12 is not limited to a substantially circular shape, and can be appropriately determined according to the planar shape of the electrode pad 13.
  • the planar shape of the sintered body 12 may be, for example, a polygonal shape such as a substantially rectangular shape, or a shape such as a substantially elliptical shape or a substantially oval shape.
  • the upper surface 12b of the sintered body 12 has a concave shape recessed on the base material 11 side (see FIGS. 1 (D) and 3 (D)).
  • the concave shape preferably has a substantially hemispherical shape.
  • the contact area between the upper surface 12b of the sintered body 12 and the second bonding layer described later becomes wide, and when shear stress is applied from the side surface of the conductive pillar, the interface with the second bonding layer is reached. Is less likely to break, and the bondability between the sintered body 12 and the second bonding layer becomes even better.
  • the base material 11 and the member to be joined are joined with higher joining strength, which is preferable.
  • the upper surface 12b of the sintered body 12 is formed with a plurality of groove portions 12a extending from the upper surface 12b toward the base material 11 (see FIGS. 1 (D) and 3 (D)).
  • the material to be the bonding layer which will be described later, melts into the groove portions 12a and then hardens to form an anchor portion.
  • the bondability between the sintered body 12 and the bonding layer is further improved, and the base material 11 and the member to be bonded to be bonded to the base material 11 are bonded with higher bonding strength, which is preferable.
  • the sintered body 12 is made of a sintered body of copper fine particles having an average particle diameter of less than 1 ⁇ m, and has a porous structure in which the copper fine particles are fused by sintering.
  • the measured value measured by the small-angle X-ray scattering measurement method (Small-Angle X-ray Scattering, SAXS) is used.
  • the conductive pillar 1 is a sintered body 12 of copper fine particles having an average particle diameter of less than 1 ⁇ m, it has a high density and good conductivity containing copper fine particles. Further, when the conductive pillar 1 is a sintered body 12 of copper fine particles having an average particle diameter of less than 1 ⁇ m, for example, the sintered body 12 is substantially cylindrical and has a diameter of 100 ⁇ m or less that can correspond to the miniaturization of the bonded structure. Even if it is small, it has sufficient conductivity by containing a sufficient number of copper fine particles at a high density. Therefore, the conductive pillar 1 of the present embodiment can cope with the miniaturization of the joint structure.
  • the conductive pillar 1 is a sintered body 12 of copper fine particles having an average particle diameter of less than 1 ⁇ m
  • the surface of the sintered body 12 is compared with the case of a sintered body of copper fine particles having an average particle diameter of 1 ⁇ m or more.
  • the surface area of the copper fine particles exposed to is increased. Therefore, the bondability and electrical connection between the sintered body 12 and the electrode pad 13 and the second bonding layer described later are improved.
  • the conductive pillar 1 is a sintered body 12 of copper fine particles having an average particle diameter of less than 1 ⁇ m
  • the shape of the conductive pillar 1 can be formed by the fusion function of the copper fine particles obtained by sintering.
  • the average particle size of the copper fine particles is 1 ⁇ m or more, it is difficult to form the shape of the conductive pillar by using the fusion function between the copper fine particles by sintering. Therefore, when the average particle size of the copper fine particles is 1 ⁇ m or more, it is necessary to contain a pineapple resin for joining the copper fine particles in the conductive pillar. Therefore, when the average particle size of the copper fine particles is 1 ⁇ m or more, the heat resistance performance is inferior to that of the conductive pillar 1 of the present embodiment.
  • the conductive pillar 1 is a sintered body 12 of copper fine particles having an average particle diameter of 100 nm or less measured using SAXS.
  • the conductive pillar 1 is made of a sintered body 12 having a higher density and containing the copper fine particles and having a wider surface area of the copper fine particles exposed on the surface, which is preferable.
  • the metal species used as the copper fine particles may be only one type of Cu, may be a mixture of one or more types of metal elements other than Cu, or may contain one or more types of metal elements other than Cu. It may be an alloy.
  • the method for producing the conductive pillar 1 of the present embodiment includes a step of forming a columnar body on the base material 11 using copper fine particles having an average primary particle diameter of less than 1 ⁇ m, and a step of sintering the columnar body to obtain an upper surface 12b. It has a step of forming a sintered body 12 having a concave shape recessed on the base material 11 side. Therefore, according to the method for manufacturing the conductive pillar 1 of the present embodiment, the conductive pillar 1 can be manufactured without using the electroplating method.
  • a copper pillar is formed on a base material by an electroplating method
  • plating is performed when the plating base layer arranged under the resist layer is etched and removed after the copper pillar is formed. In some cases, a part of the base material was removed together with the base layer. Further, when the copper pillars are formed by the electroplating method, the cost of introducing the equipment necessary for forming the copper pillars is high, and the environmental load due to the harmful waste liquid is also large.
  • Step to remove residue> After the step of sintering the copper fine particle paste, it is preferable to further include a step of removing the residue of the copper fine particle paste remaining on the surface of the outermost layer on the base material. In the step of sintering the copper fine particle paste, the residue of the copper fine particle paste may remain on the surface of the resist layer.
  • the material 22a to be the second bonding layer 22 which will be described later, is supplied to the concave shape recessed on the base material 11 side of the sintered body 12 shown in FIG. 1 (D) or FIG.
  • the resist layer 16 Since the difference in surface energy between the upper part of the resist layer 22 and the material 22a to be the second bonding layer 22 is small, the material 22a to be the second bonding layer 22 is placed on the entire surface including the upper part of the resist layer 16, and FIG. As shown in 8 (A), it becomes difficult to form the second bonding layer 22 in a convex shape.
  • a step of removing the residue of the copper fine particle paste remaining on the surface of the resist layer is provided, so that the resist layer 16 and the material 22a to be the second bonding layer 22 are provided.
  • the second bonding layer 22 has a shape that is raised in a convex curved surface shape due to the large difference in surface energy between the two and the bonding layer 22.
  • Examples of the method for removing the residue of the copper fine particle paste remaining on the surface of the resist layer include a physical method such as chemical mechanical polishing (CMP), wet etching for dissolving a component to be dissolved in a liquid, and a reactive gas.
  • CMP chemical mechanical polishing
  • Chemical methods such as dry etching that etches the material with (etching gas), ions, and radicals can be applied.
  • wet etching is preferable in which a component that dissolves in the acid or alkali is dissolved in contact with the acid or alkali, and a known and publicly available substance can be used as the copper etching solution.
  • an etching agent containing hydrogen peroxide, hydrogen peroxide, azoles, and an etching solution containing bromine ions Japanese Patent Laid-Open No. 2006-13340
  • hydrogen peroxide, hydrogen peroxide, and a benzotriazole derivative specifically. Kai 2009-149971
  • an etching solution containing hydrogen peroxide and sulfuric acid as main components and azoles as additives Japanese Patent Laid-Open No. 2006-9122
  • hydrogen peroxide, sulfuric acid and aminotetrazole and an etching solution containing phenylurea (Japanese Patent Laid-Open No.
  • the paste and the Cu thin film 17a above the resist layer shown in FIG. 3 (D) are shown in FIG.
  • the residue of the copper fine particle paste is removed, the Cu thin film 17b on the side surface of the sintered body and the Cu thin film 17c on the electrode pad remain because they are embedded in the resist layer 16.
  • the Cu thin film 17d when the Cu thin film 17d is formed in the lower part of the resist layer, the Cu thin film 17d is simultaneously used in the step of removing the residue of the copper fine film paste remaining on the surface of the outermost layer on the substrate. Since it cannot be removed, both a step of removing the copper fine film paste 12c remaining on the upper part of the resist layer and a step of removing the Cu thin film 17d on the lower part of the resist layer are required.
  • the method for producing the conductive pillar 1 according to the second embodiment having the Cu thin film 17a on the upper part of the resist layer is the surface of the outermost layer including the surface of the resist layer on the base material after the step of sintering the copper fine particle paste.
  • the Cu thin film 17a on the upper part of the resist layer can be removed at the same time in the step of removing the residue of the copper fine particle paste remaining in the copper fine particle paste, the copper fine particles remaining on the upper part of the resist layer before the step of sintering the copper fine particle paste.
  • the step of removing the paste 12c can be omitted.
  • Step of removing the resist layer and the exposed Cu thin film> In the method for producing a conductive pillar according to the first embodiment, after the step of sintering the copper fine particle paste, the resist layer is further removed as shown in FIG. 2, and then the exposed Cu thin film is removed.
  • a process can be provided. First, the resist layer 16 provided on the base material 11 shown in FIG. 1D via the Cu thin film 17d under the resist layer 16 is removed, and the Cu thin film 17d under the resist layer 16 is removed. To expose. As a method for removing the resist layer 16, a known method can be used. Next, the exposed Cu thin film 17d is removed to expose the base material 11 as shown in FIG.
  • Examples of the method for removing the exposed Cu thin film 17d include the same methods as described as the method for removing the residue of the copper fine particle paste.
  • a conductive pillar 1 composed of a sintered body 12 of copper fine particles provided on the electrode pad 13 on the base material 11 via a first bonding layer 17c made of a Cu thin film 17 can be obtained. ..
  • the upper surface of the sintered body 12 has a concave shape recessed toward the base material 11.
  • the Cu thin film can be thinned. Since the Cu thin film and the conductive pillar are made of the same copper, the conductive pillar may be thinned by etching. However, in the present embodiment, since the Cu thin film under the resist layer can be thinned, there is little possibility that the conductive pillars become thin due to etching when the Cu thin film is removed. Further, since the Cu thin film and the conductive pillar are etched in the same manner, undercut does not occur. When a Ti thin film is formed under the copper plating base layer, the Ti thin film under the copper pillar is also etched when the exposed Ti thin film is etched after the resist layer is removed, resulting in undercut. It will occur.
  • the Cu is more than the conventional case where the copper plating base layer is formed under the resist layer and the copper pillars are formed by the electroplating method. Since the thin film and the Ti thin film can be made thin, there is little possibility that undercut will occur at the base of the conductive pillar.
  • the sintered body 12 of the copper fine particles is formed directly on the first bonding layer 17c made of the Cu thin film on the electrode pad 13, so that the first bonding layer 17c Can be firmly bonded to the sintered body 12. Further, since the conductive pillar 1 is less likely to cause undercut at the root, it is possible to form a conductive pillar having a fine shape with good stability. Further, it can be expected that the base material 11 and the member to be bonded can be bonded with high bonding strength via the second bonding layer 22.
  • ⁇ Step of removing the resist layer> In the method for producing a conductive pillar according to the second embodiment, after the step of sintering the copper fine particle paste, as shown in FIG. 5, a step of further removing the resist layer can be provided.
  • the resist layer 16 provided directly on the base material 11 shown in FIG. 4.0 cm is removed to expose the base material 11 as shown in FIG.
  • the resist layer 16 is composed of a sintered body 12 of metal fine particles provided on the base material 11 via an electrode pad 13, and the upper surface of the sintered body 12 has a concave shape recessed toward the base material 11 and is sintered.
  • a conductive pillar 1 whose side surface of the body 12 is covered with a Cu thin film 17b can be obtained.
  • the plating base layer is not arranged under the resist layer as in the case of forming copper pillars by the electroplating method, it is necessary to remove the plating base layer by etching in the step of removing the resist layer of the present embodiment. There is no risk of undercutting at the base of the conductive pillar 1. Further, the resist layer 16 can be removed while leaving the Cu thin film 17b on the side surface of the sintered body.
  • the resist layer 16 is directly formed from the state where the Cu thin film 17 is formed on the surface of the resist layer 16 shown in FIG. 3 (D). It may be removed.
  • a known method can be used. Since the conductive pillar 1 obtained here has no undercut and the side surface of the sintered body 12 is covered with the Cu thin film 17b, the base material 11 and the member to be joined are highly bonded via the bonding layer. Can be joined with strength. Further, it can be expected that a conductive pillar having a fine shape can be formed with good stability.
  • 6 and 8 are process diagrams for explaining an example of a method for manufacturing a bonded structure.
  • the method for manufacturing the bonded structure described in FIGS. 6 (C) and 8 (C) will be described in detail below.
  • the method for manufacturing the bonded structure described in FIG. 6 is defined as the third embodiment
  • the method for manufacturing the bonded structure described in FIG. 8 is defined as the fourth embodiment.
  • the material 22a to be the second bonding layer 22 is supplied to the surface and melted (reflowed) to solidify.
  • a bump made of the second bonding layer 22 is provided along the concave shape of the sintered body 12.
  • the obtained second bonding layer 22 has a convex curved surface shape due to a large surface energy difference between the resist layer 16 and the material 22a serving as the second bonding layer 22. It will have a raised shape.
  • a plurality of groove portions 12a extending from the upper surface 12b toward the base material 11 are formed on the upper surface 12b of the sintered body 12. Therefore, by melting (reflowing) the material 22a to be the second bonding layer 22, the material 22a to be the second bonding layer 22 enters the groove 12a and is filled in the groove 12a to form an anchor portion. NS. Further, the molten material 22a to be the second bonding layer 22 also enters the porous structure of the sintered body 12 and solidifies.
  • the material 22a to be the second bonding layer 22 supplied to the concave shape of the sintered body 12 forms the intermetallic compound layer 25 with the copper fine particles in the sintered body 12. Since the sintered body 12 has a porous structure, it has a large specific surface area. Therefore, in the present embodiment, the intermetallic compound layer 25 is formed more quickly than, for example, as compared with the case where the conductive pillar is made of a dense bulk metal formed by an electroplating method or the like.
  • the bonded layer 22 is formed in a concave shape recessed on the base material 11 side of the sintered body 12 shown in FIG. Material 22a is supplied and melted (reflowed) to solidify. As a result, a bump made of the bonding layer 22 is provided along the concave shape of the sintered body 12. As shown in FIG. 8A, the obtained bonding layer 22 has a convex curved surface shape due to a large difference in surface energy between the resist layer 16 and the material 22a serving as the bonding layer 22. It becomes.
  • a plurality of groove portions 12a extending from the upper surface 12b toward the base material 11 are formed on the upper surface 12b of the sintered body 12. Therefore, by melting (reflowing) the material 22a to be the bonding layer 22, the material 22a to be the bonding layer 22 enters the groove 12a and is filled in the groove 12a to form an anchor portion. Further, the molten material 22a to be the bonding layer 22 also enters the porous structure of the sintered body 12 and solidifies.
  • the material 22a to be the bonding layer 22 supplied in the concave shape of the sintered body 12 forms the intermetallic compound layer 25 with the copper fine particles in the sintered body 12. Since the sintered body 12 has a porous structure, it has a large specific surface area. Therefore, in the present embodiment, the intermetallic compound layer 25 is formed more quickly than, for example, as compared with the case where the conductive pillar is made of a dense bulk metal formed by an electroplating method or the like.
  • Examples of the method of supplying the material 22a to be the second bonding layer 22 to the concave shape of the sintered body 12 include a printing method such as a stencil mask method and a dry film method, a ball mounting method, a vapor deposition method, and a molten solder injection method. (IMS method) and the like can be used. Among these, as shown in FIGS. 6A and 8A, it is preferable to use the IMS method of embedding the molten solder in the concave shape of the sintered body 12 using the injection head 22b. By using the IMS method, the solder which is the material 22a to be the second bonding layer 22 can be supplied to the concave shape of the sintered body 12 in a molten state, which is preferable.
  • the third embodiment can include a step of removing the Cu thin film 17d under the resist layer 16 and the exposed resist layer 16.
  • the resist layer 16 provided on the base material 11 shown in FIG. 6A via the Cu thin film 17d under the resist layer 16 is removed to remove the Cu thin film 17d under the resist layer 16.
  • a method for removing the resist layer 16 a known method can be used.
  • the exposed Cu thin film 17d is removed to expose the base material 11 as shown in FIG. 6 (B). Examples of the method for removing the exposed Cu thin film 17d include the same methods as described as the method for removing the residue of the copper fine particle paste.
  • a conductive pillar 1 composed of a sintered body 12 of copper fine particles provided on the electrode pad 13 on the base material 11 via a first bonding layer 17c made of a Cu thin film 17 can be obtained. ..
  • the conductive pillar 1 obtained here has a concave shape in which the upper surface of the sintered body 12 is recessed toward the base material 11, and is a bump formed of a second bonding layer 22 along the concave shape of the sintered body 12. Is provided.
  • the third embodiment unlike the case where the copper pillar is formed by the electroplating method, it is not necessary to apply an electric potential to the plating base layer under the resist layer, and it is not necessary to pass a uniform current.
  • the Cu thin film under the layer can be thinned.
  • the conductive pillars are less likely to be thinned by etching, and the roots of the conductive pillars 1 are less likely to be undercut.
  • the conductive pillar 1 obtained here is less likely to cause undercut, it is possible to form a conductive pillar having a fine shape with good stability. Further, it can be expected that the base material 11 and the member to be bonded can be bonded with high bonding strength via the second bonding layer 22.
  • the resist layer 16 is removed.
  • a known method can be used.
  • the resist layer 16 provided directly on the base material 11 shown in FIG. 8 (A) is removed to expose the base material 11 as shown in FIG. 8 (B).
  • a conductive pillar composed of a sintered body 12 of metal fine particles provided on the base material 11 via an electrode pad 13 can be obtained.
  • the conductive pillar obtained here has a concave shape in which the upper surface of the sintered body 12 is recessed toward the base material 11, and bumps made of the bonding layer 22 are provided along the concave shape of the sintered body 12.
  • the side surface of the sintered body 12 is covered with the Cu thin film 17b.
  • the plating base layer is not arranged under the resist layer as in the case of forming copper pillars by the electroplating method, so that multi-step etching is performed. Since the resist layer 16 can be removed in one step without the need for the above, there is no possibility of undercut between the electrode pad 13 and the sintered body 12, and a fine column-shaped fine copper pillar is formed. be able to.
  • the resist layer 16 can be removed leaving the Cu thin film 17b on the side surface of the sintered body.
  • the method for manufacturing the conductive pillars of the second embodiment is as follows, as shown in FIG. 9B described later, the conductive pillars 1a, 1b, and 1c having different planar shapes have different sizes. There is an advantage that it can be formed at one time, or a plurality of conductive pillars having different planar shapes can be formed at one time. Since the conductive pillars obtained here have no undercut and the side surfaces of the sintered body 12 are covered with the Cu thin film 17b, the conductive pillars having a fine shape can be formed with good stability. Further, it can be expected that the base material 11 and the member to be joined can be joined with high joining strength via the joining layer 22.
  • the resist layer 16 is removed after the bonding layer 22 is formed has been described as an example, but the resist layer 16 does not have to be removed after the bonding layer 22 is formed.
  • the resist layer 16 is arranged between the base material 11 and the member to be joined by laminating the base material 11 and the member to be joined, which will be described later.
  • the base material 11 and the member to be joined 21 are electrically connected by the flip chip mounting method. Specifically, as shown in FIGS. 6 (C) and 8 (C), the base material 11 on which the second bonding layer 22 is formed on the sintered body 12 and the member to be bonded 21 are arranged to face each other. And stack. In the fourth embodiment, the surface of the member to be joined 21 where the electrode 23 is provided is arranged upward, and the surface of the base material 11 on which the second bonding layer 22 is formed is arranged downward. Then, the electrode 23 of the member to be joined 21 and the second bonding layer 22 of the base material 11 are overlapped with each other.
  • the base material 11 and the member to be joined 21 are heated in a laminated state to melt the second joining layer 22, the base material 11 and the member to be joined 21 are joined, and the second joining layer 22 is solidified. Let me. By the above steps, the joint structure 20 is obtained.
  • the conductive pillar 1 is composed of a sintered body 12 of copper fine particles provided on an electrode pad 13 on a base material 11 via a first bonding layer 17c made of a Cu thin film 17. Since the sintered body 12 of the copper fine particles is formed directly on the first bonding layer 17c made of the Cu thin film on the electrode pad 13, the space between the first bonding layer 17c and the sintered body 12 is strong. Can be combined with.
  • the sintered body 12 has an average particle diameter of less than 1 ⁇ m measured using SAXS of copper fine particles, and the upper surface 12b (lower surface in FIGS. 6C and 8C) of the sintered body 12 is a base material. It has a concave shape that is recessed on the 11 side.
  • the second bonding layer 22 that has entered the concave shape of the conductive pillar 1 is formed.
  • the sintered body 12 of the copper fine particles has an average particle size of less than 1 ⁇ m measured using SAXS, and has a porous structure in which the copper fine particles are fused by sintering. Therefore, when the second bonding layer 22 is formed, the molten material 22a to be the second bonding layer 22 enters the porous structure of the sintered body 12 and solidifies.
  • the conductive pillar 1 of the first embodiment has a large bonding area with the second bonding layer 22, for example, the upper surface is made a flat surface parallel to the base material by being formed by an electroplating method. It is bonded to the second bonding layer 22 with a high bonding strength (share strength) as compared with a conductive pillar made of a dense metal. As a result, according to the conductive pillar 1 of the first embodiment, the base material 11 and the member to be bonded 21 can be bonded with a high bonding strength (share strength) via the second bonding layer 22.
  • the conductive pillar 1 is made of a sintered body 12 of copper fine particles having an average particle diameter of less than 1 ⁇ m, and has a porous structure in which the copper fine particles are fused by sintering. Therefore, the conductive pillar 1 is formed by an electroplating method or the like. Compared with dense bulk metal, stress caused by the difference in thermal expansion rate can be relaxed, and excellent durability can be obtained.
  • the bonding structure 20 is arranged between the base material 11 and the member to be bonded 21, and has a conductive pillar 1 and a second bonding layer 22 provided along the concave shape of the conductive pillar 1. Therefore, in the bonding structure 20 of the first embodiment, the second bonding layer 22 is inserted into the concave shape of the conductive pillar 1, and the base material 11 and the member to be bonded 21 are connected to each other via the second bonding layer 22. Is joined with high joining strength.
  • the material of the second bonding layer 22 As the material of the second bonding layer 22, Au, Ag, Cu, Sn, Ni, a solder alloy or the like can be used, and an alloy containing one or more metals selected from Sn, Pb, Ag and Cu. Is preferably used.
  • the second bonding layer 22 may be formed of only a single component or may contain a plurality of components.
  • the solder alloy used as the material of the second bonding layer 22 include Sn—Ag alloy, Sn—Pb alloy, Sn—Bi alloy, Sn—Zn alloy, Sn—Sb alloy, Sn—Bi alloy, Sn—In alloy, and the like.
  • Sn—Cu alloys alloys in which two elements selected from the group consisting of Au, Ag, Bi, In and Cu are added to Sn can be used.
  • FIGS. 6 (C) and 8 (C) are cross-sectional views showing an example of the joint structure obtained by the method for manufacturing the joint structure.
  • the bonding structure 20 shown in FIGS. 6 (C) and 8 (C) includes a base material 11, the conductive pillar 1, and a second bonding layer 22 provided along the concave shape of the conductive pillar 1. It has a member 21 to be joined. Since the sintered body 12 of the copper fine particles is formed directly on the first bonding layer 17c made of the Cu thin film on the electrode pad 13, the space between the first bonding layer 17c and the sintered body 12 is strong. Can be combined with.
  • the first bonding layer 17c made of the Cu thin film 17 and the sintered body 12 are firmly bonded to each other, so that the strength of the conductive pillar 1 and the bonding structure 20 can be improved. It is presumed to be.
  • a plurality of conductive pillars 1 extending from the upper surface 12b (lower surface in FIGS. 6 (C) and 8 (C)) toward the base material 11.
  • a part of the second bonding layer 22 is filled in the groove portion 12a of the above to form an anchor portion. Therefore, in the bonding structure 20 shown in FIGS. 6 (C) and 8 (C), the sintered body 12 of the conductive pillar 1 and the second bonding layer 22 are bonded with a higher bonding strength (share strength). It becomes a thing.
  • the bonding structure 20 shown in FIGS. 6 (C) and 8 (C) has an intermetallic compound layer 25 at the interface between the conductive pillar 1 and the second bonding layer 22.
  • the intermetallic compound layer 25 improves the bonding strength (share strength) between the conductive pillar 1 and the second bonding layer 22.
  • the components in the second bonding layer 22 are diffused toward the inside of the conductive pillar 1, and the copper fine particle components in the sintered body 12 are directed toward the inside of the second bonding layer 22. It is formed by diffusing. Therefore, the composition of the intermetallic compound layer 25 changes depending on the metal species forming the sintered body 12 and the second bonding layer 22 and the sintering conditions.
  • the base material 11 and the member to be bonded 21 are arranged so as to face each other.
  • the member 21 to be joined is not limited as long as it is a substrate on which an arbitrary electric circuit is formed and the electrode 23 is provided on the surface.
  • a glass substrate, a ceramic substrate, a Si substrate such as a Si interposer, a resin substrate, a printed wiring board, or the like can be used, and a bonding structure 20 having a fine conductive pillar 1 can be produced.
  • a glass substrate, a ceramics substrate, or a Si substrate having excellent dimensional stability can be preferably selected.
  • the bonding structure 20 has a conductive pillar 1 of the present embodiment and a second bonding layer 22 provided along the concave shape of the conductive pillar 1.
  • the conductive pillar 1 shown in FIG. 1 (D) is installed in a state where the vertical direction in FIG. 1 (D) is inverted, and the joint structure 20 shown in FIG. 9 is installed. Then, the conductive pillar 1 shown in FIG.
  • FIG. 3 (D) is installed in a state where the vertical direction in FIG. 3 (D) is inverted.
  • the case where the second bonding layer 22 has a single-layer structure made of one type of material will be described as an example, but the second bonding layer has a multi-layer structure in which two or more types of materials are laminated. You may.
  • FIGS. 7 (A) and 9 (A) are cross-sectional views showing an example of the joint structure obtained by the method for manufacturing the joint structure of the present embodiment.
  • the sealing resin 26 is filled in the region where the bonding structure 20 is not arranged between the base material 11 and the member 21 to be bonded.
  • a filling method of the sealing resin 26 a conventionally known method can be used.
  • the area where the bonding structure 20 is not arranged between the base material 11 and the member 21 to be bonded is filled with the sealing resin 26.
  • the material of the sealing resin 26 conventionally known materials such as epoxy resin can be used.
  • FIG 7 (A) and 9 (A) are cross-sectional views showing another example of the joint structure obtained by the method for manufacturing the joint structure of the present embodiment.
  • the case where the three bonding structures 20 in which the base material 11 and the member to be bonded 21 are arranged to face each other have substantially the same shape is taken as an example.
  • some or all of the plurality of bonding structures may have different shapes. That is, the shapes of the conductive pillars and the second bonding layer of each bonding structure can be appropriately determined according to the planar shapes of the electrode pads of the base material 11 and the electrodes of the member 21 to be bonded.
  • FIG. 7B is a cross-sectional view showing another example of the joining structure of the present embodiment.
  • FIG. 9B is a cross-sectional view showing another example of the joining structure of the present embodiment.
  • FIGS. 7 (B) and 9 (B) a plurality of (three in the examples shown in FIGS. 7 (B) and 9 (B)) are joined between the base material 11 and the member to be joined 21.
  • Structures 20a, 20b, 20c are provided.
  • the planar shape of one of the three joint structures 20a, 20b, 20c is the other joint structures 20b, 20c.
  • the other joint structures 20b and 20c have the same shape.
  • the shape is larger than the other electrode pads 13 and electrodes 23.
  • the outer diameter (diameter) of the substantially columnar conductive pillar 1a of the joint structure 20a is made larger than that of the other conductive pillars 1b and 1c.
  • the size of the second bonding layer 22 included in the bonding structure 20a is also larger than that of the second bonding layer 22 included in the other bonding structures 20b and 20c.
  • the distance between the base material 11 and the member to be joined 21 is substantially constant, and the base material 11 in the three joint structures 20a, 20b, and 20c The length in the thickness direction is almost the same.
  • the three bonding structures 20a, 20b, and 20c shown in FIGS. 7B and 9B have shapes corresponding to the outer shapes of the conductive pillars 1a, 1b, and 1c in the step of patterning the resist layer 16, respectively. It can be produced at the same time by using the same method as the three bonding structures 20 shown in FIGS. 7 (A) and 9 (A) described above except that the resist opening is formed. Therefore, there are cases where the three joint structures 20a, 20b, and 20c shown in FIGS. 7 (B) and 9 (B) are manufactured, and cases where the three joint structures 20 shown in FIGS. 7 (A) and 9 (A) are manufactured. There is no difference in the dimensional accuracy of the obtained joint structure and the number of manufacturing steps.
  • FIGS. 7B and 9B three bonding structures 20a, 20b and 20c arranged between the base material 11 and the member to be joined 21 are shown, but the base material 11 and the material to be joined are shown.
  • the number of the joining structures 20a, 20b, and 20c arranged between the joining member 21 is not limited to three, and for example, only two of the joining structure 20a and the joining structure 20b may be used. It may be four or more, and is determined as needed.
  • FIGS. 7 (B) and 9 (B) the case where the planar shapes of the conductive pillars 1a, 1b, and 1c are all substantially circular has been described as an example, but the planar shape of each conductive pillar has been described. Is not limited to a substantially circular shape, and can be appropriately determined according to the planar shape of the electrode pad 13. Further, in FIGS. 7 (B) and 9 (B), the case where the lengths of the base materials 11 in the thickness direction in the three bonded structures 20a, 20b, and 20c are substantially the same has been described as an example. The length of the base material 11 of the bonded structure in the thickness direction may be partially or completely different.
  • An electronic device including the joint structure 20 can be manufactured by the method for manufacturing the joint structure of the present embodiment.
  • the electronic device of the present embodiment preferably includes a plurality of bonding structures 20.
  • a part or all of the plurality of joint structures 20 may have different shapes.
  • a device having a three-dimensional (3D) mounting structure including a plurality of bonding structures 20 of the present embodiment, or an interposer including a plurality of bonding structures 20 of the present embodiment is used as the electronic device of the present embodiment. Examples include devices having a 2.5-dimensional (2.5D) mounting structure. Since the electronic device of the present embodiment includes the bonding structure 20 of the present embodiment, the base material 11 and the member to be bonded 21 are bonded with high bonding strength.
  • the obtained reaction mixture was circulated in a hollow fiber type ultrafiltration membrane module (HIT-1-FUS1582 , 145 cm 2 , fractional molecular weight 150,000) manufactured by Daisen Membrane Systems Co., Ltd., and the filtrate was leached out.
  • a hollow fiber type ultrafiltration membrane module HIT-1-FUS1582 , 145 cm 2 , fractional molecular weight 150,000
  • the mixture was circulated and purified until the filtrate from the ultrafiltration module became about 500 mL.
  • the supply of the 0.1% hydrazine hydrate aqueous solution was stopped, and the mixture was concentrated as it was by the ultrafiltration method to obtain an aqueous dispersion of a composite of an organic compound containing 2.85 g of thioether and copper fine particles.
  • the non-volatile content in the aqueous dispersion was 16%.
  • thermogravimetric analysis > 2 to 25 mg of the synthesized dry powder of the copper fine particle composite was precisely weighed on an aluminum pan for thermogravimetric analysis and placed on an EXSTAR TG / DTA6300 type differential thermal weight analyzer (manufactured by SII Nanotechnology Co., Ltd.). Then, in an inert gas atmosphere, the temperature was raised from room temperature to 600 ° C. at a rate of 10 ° C. per minute, and the weight loss rate of 100 ° C. to 600 ° C. was measured. From the results, it was confirmed that an organic substance containing a 3% polyethylene oxide structure was present in the dry powder of the copper fine particle complex.
  • the average primary particle size of the synthesized copper fine particle composite was measured by transmission electron microscopy (TEM) observation.
  • TEM transmission electron microscopy
  • the dried powder of the synthesized copper fine particle complex was diluted 100-fold with water to prepare a dispersion.
  • the dispersion was cast on a carbon film-coated grid, dried, and observed with a transmission electron microscope (device: TEMJEM-1400 (manufactured by JEOL), acceleration voltage: 120 kV).
  • 200 copper fine particle composites were randomly extracted from the obtained TEM images, the areas of each were calculated, and the particle size when converted to a true sphere was calculated based on the number of particles, and the average primary particle size was calculated. did.
  • the average primary particle size of the synthesized copper fine particle complex was 42 nm.
  • a sintered body of the copper fine particle paste obtained by the above method was prepared by simulating the method for producing the conductive pillars of the examples described later. Specifically, the copper fine particle paste obtained by the above method was uniformly applied onto a silicon wafer in an argon gas atmosphere so as to have a film thickness of 1 mm.
  • calcination was performed to volatilize the solvent in the copper fine particle paste coated on the silicon wafer at a low temperature.
  • the tentative firing was performed by heating a silicon wafer coated with the copper fine particle paste at 120 ° C. for 5 minutes using a tabletop vacuum solder reflow device (manufactured by Unitemp) in a nitrogen gas atmosphere.
  • the copper fine particle paste coated on the silicon wafer was sintered to form a sintered body.
  • the copper fine particle paste was sintered by heating the silicon wafer after pre-baking at 250 ° C. for 10 minutes using a tabletop vacuum solder reflow device (manufactured by Unitemp) in a nitrogen atmosphere containing formic acid vapor. ..
  • the obtained sintered body was scraped off from the silicon wafer, and the powder of the copper fine particle sintered body was collected.
  • the average particle size of the collected copper fine particle sintered body was measured by the small-angle X-ray scattering measurement method (SAXS). The result can be regarded as the average particle size of the metal fine particles forming the conductive pillars of the examples described later.
  • An X-ray diffractometer (trade name: SmartLab) manufactured by Rigaku Co., Ltd. was used for measuring the average particle size of the copper fine particles in the sintered body. The measurement was performed in the step mode with the diffraction angle 2 ⁇ in the range of 0 to 4 °. The step angle was 0.005 ° and the measurement time was 5 seconds.
  • the average particle size of the copper fine particles was estimated by calculating the measurement data obtained by SAXS using analysis software (NANO-Solver Ver.3). The result is shown in FIG. FIG. 10 is a graph showing the particle size distribution of the copper fine particles. As shown in FIG. 10, the particle size of the copper fine particles in the sintered body is 322 nm (distribution 1) with a volume fraction of 6%, 45 nm (distribution 2) with a volume fraction of 91%, and 15 nm with a volume fraction of 4%. It was (distribution 3). From this result, the average particle size of the copper fine particles in the sintered body was estimated to be 59.112 nm.
  • Example 1 ⁇ Manufacturing conductive pillars> Ar gas is used on a silicon wafer (base material 11) having a diameter of 4 inches provided with an electrode pad 13 made of Al, and Ar positive ions are collided with each other to reverse-sputter and clean the film. A 250 nm Cu thin film 17 was formed (FIG. 1A).
  • the resist was exposed and developed, and a plurality of opening patterns were formed in the resist layer 16 so that the openings 16a were provided on the Al electrode pads (FIG. 1 (B)).
  • the shape of the opening pattern of the resist layer 16 consists of a cylindrical shape with a diameter of 30 to 75 ⁇ m on the top and bottom surfaces and a square prismatic recess with a side of 30 to 75 ⁇ m on the top and bottom surfaces, and the depth of the opening is It was 30 ⁇ m.
  • the aspect ratio (depth: diameter) of the cylindrical opening was designed to be 1.0: 1.0 to 2.5.
  • the copper fine particle paste obtained by the above method is filled in the cylindrical and square pillar-shaped openings by the method shown below, and the copper fine particle paste 12c is formed in the opening 16a on the base material 11.
  • a columnar body was formed (FIG. 1 (C)).
  • the copper fine particle paste was filled in an argon gas atmosphere.
  • the copper fine particle paste is placed on the substrate, and the squeegee installed in the semi-automatic screen printing device (made by Ceria) is swept back and forth on the substrate at an attack angle of 70 ° and a moving speed of 10 mm / s. It was carried out by the method of coating.
  • As the squeegee a square squeegee made of urethane rubber having a hardness of 70 ° was used.
  • the base material on which the columnar body composed of the copper fine particle paste 12c was formed was exposed for 10 minutes in an environment of a temperature of 250 ° C. using a hot plate in a nitrogen gas atmosphere containing formic acid vapor.
  • the copper fine particle paste was sintered (FIG. 1 (D)).
  • the base material filled with the conductive paste and sintered was immersed in a copper etching agent (WLC-C2 manufactured by Ryoe Chemical Co., Ltd.) for 30 seconds to leave the copper fine particle paste on the surface of the outermost layer on the base material. Residue was removed. Through the above steps, the conductive pillar of Example 1 was obtained (FIG. 1 (D)).
  • a copper etching agent WLC-C2 manufactured by Ryoe Chemical Co., Ltd.
  • the conductive pillar of Example 1 is copper provided on the electrode pad 13 on the base material 11 via a first bonding layer 17c made of a Cu thin film 17. It is composed of a sintered body 12 of fine particles.
  • the sintered body 12 has a porous structure in which copper fine particles are fused by sintering, and has a concave shape in which the upper surface 12b is recessed toward the base material 11.
  • FIG. 11 is a micrograph of a cross section of the conductive pillar of Example 1 in which the shape of the opening pattern is a cylindrical shape having a diameter of 50 ⁇ m on the upper surface and the bottom surface.
  • FIG. 12 is a photomicrograph of the upper surface of the conductive pillar shown in FIG.
  • reference numeral 11 indicates a base material
  • reference numeral 12 indicates a sintered body
  • reference numeral 12b indicates an upper surface of the sintered body
  • reference numeral 13 indicates an electrode pad.
  • the conductive pillar (sintered body 12) of the example had a concave shape in which the upper surface 12b was recessed toward the base material 11.
  • Example 2 ⁇ Manufacturing conductive pillars>
  • an IMS (Injection Soldering) method (see, for example, Japanese Patent Application Laid-Open No. 2015-106617) is applied to a concave shape recessed on the substrate side of the sintered body forming the conductive pillar of Example 1.
  • molten solder SAC305
  • the molten solder was supplied as the material 22a to be the second bonding layer 22, and bumps were provided along the concave shape of the sintered body.
  • the molten solder was directly injected and supplied from the injection head 22b (reservoir) holding the molten solder to the opening portion (FIG. 6 (A)).
  • SAC305 was used as the solder alloy.
  • a second bonding layer (bump) made of a solder alloy was produced.
  • the obtained second bonding layer had a raised shape like a convex curved surface.
  • the resist layer was removed. Further, by immersing in a copper etching agent (WLC-C2 manufactured by Ryoe Chemical Co., Ltd.) for 15 seconds, the Cu thin film 17d under the resist layer 16 exposed on the substrate is removed by etching, and the conductive pillar of Example 2 is removed. Was obtained (Fig. 6 (B)).
  • the conductive pillar of Example 2 is provided on an Al electrode pad on a base material via a Cu thin film (first bonding layer 17c) having a thickness of 250 nm, and the height of the pillar (the height of the sintered body).
  • the thickness was 15 to 20 ⁇ m
  • the thickness of the intermetallic compound layer was 1 to 5 ⁇ m
  • the height of the second bonding layer was about 5 to 15 ⁇ m.
  • the diameter of the conductive pillar is almost the same as the diameter of the opening pattern of the resist layer.
  • the Cu thin film and the conductive pillar are formed of the same Cu. Therefore, undercut does not occur when the Cu thin film is etched.
  • Example 3 ⁇ Preparation of joint structure> Next, a base material in which a second bonding layer (bump) made of a solder alloy is formed on the conductive pillar of Example 2 made of a sintered body, and a Si substrate (bonded) having an electrode made of copper on the surface.
  • the members were placed facing each other and laminated. Specifically, the electrode of the member to be joined is arranged with the surface provided with the electrode of the member to be joined facing upward, and the surface on which the second bonding layer of the base material is formed is arranged facing downward. And the second bonding layer of the base material were overlapped (FIG. 6 (C)).
  • the base material and the member to be joined were heated in a laminated state to melt the second joining layer, and the base material and the member to be joined were joined to form the joining structure of Example 3.
  • the height of the conductive pillar after chip assembly was 20 ⁇ m.
  • Example 3 (Electrical resistance measurement and insulation reliability test) Regarding the bonded structure of Example 3 in which the base material and the member to be bonded were bonded by the conductive pillar of Example 2, the electrical resistance measurement and the insulation reliability test of the conductive pillar were carried out by the evaluation method described later.
  • Example 4 ⁇ Preparation of joint structure> Then, the sealing resin is filled in the region where the bonding structure is not arranged between the base material and the member to be bonded by injecting an underfill agent made of an epoxy resin to obtain the bonding structure of Example 4. (FIGS. 7 (A) and 7 (B)).
  • a bonding structure having a sintered body 12 of conductive pillars and a second bonding layer 22 provided along the concave shape of the sintered body 12 is formed between the base material 11 and the member 21 to be bonded. (FIGS. 7 (A) and 7 (B)).
  • High temperature storage test (HTS test) A high temperature storage test (HTS test) was carried out on the joint structure of Example 4 provided with the conductive pillars of Example 2 by the evaluation method described later.
  • Example 5 ⁇ Manufacturing conductive pillars> A resist resin was applied on a silicon wafer (base material) having a diameter of 4 inches provided with an Al electrode so that the final film thickness was 30 ⁇ m. The resist was exposed and developed to form a plurality of opening patterns so that openings were provided on the Al electrode pads (FIG. 3 (A)).
  • the shape of the opening pattern consisted of a cylindrical shape with a diameter of 20 to 75 ⁇ m on the top and bottom surfaces and a square prismatic recess with a side of 20 to 75 ⁇ m on the top and bottom surfaces, and the depth of the opening was 30 ⁇ m. ..
  • the aspect ratio (depth: diameter) of the cylindrical opening was designed to be 1.0: 1.0 to 2.5.
  • the surface on the silicon wafer on which the resist layer having an opening is formed on the Al electrode is cleaned by reverse sputtering by colliding Ar plus ions with Ar gas, and then the film thickness is formed by the sputtering method.
  • a 250 nm Cu thin film was formed (FIG. 3 (B)). The shape of the opening pattern has hardly changed.
  • the copper fine particle paste obtained by the above method was filled into the openings having a columnar shape and a quadrangular prism shape to form a columnar body composed of copper fine particles on the base material (Fig.). 3 (C)).
  • the copper fine particle paste was filled in an argon gas atmosphere.
  • the copper fine particle paste is placed on the base material, and the squeegee installed in the semi-automatic screen printing device (manufactured by Ceria) is swept on the base material at an attack angle of 70 ° and a moving speed of 10 mm / s. (Fig. 3 (C)).
  • the squeegee a square squeegee made of urethane rubber having a hardness of 70 ° for screen printing was used.
  • the copper fine particle paste was sintered by exposing the base material on which the columnar body was formed to a nitrogen gas atmosphere containing formic acid vapor for 10 minutes in an environment of a temperature of 250 ° C. using a hot plate. (FIG. 3 (D)).
  • the base material filled with the conductive paste and sintered was immersed in a copper etching agent (WLC-C2 manufactured by Ryoe Chemical Co., Ltd.) for 30 seconds to leave the copper fine particle paste on the surface of the outermost layer on the base material. And the Cu thin film 17a on the upper part of the resist layer were removed.
  • a copper etching agent WLC-C2 manufactured by Ryoe Chemical Co., Ltd.
  • the conductive pillar of Example 5 is composed of a sintered body 12 of copper fine particles provided on the base material 11, and the sintered body 12 is obtained by fusing the copper fine particles by sintering. It had a porous structure, the upper surface 12b had a concave shape recessed toward the base material 11, and the side surface of the sintered body 12 was covered with a Cu thin film.
  • molten solder (SAC305) is supplied to the concave shape recessed on the base material side of the sintered body forming the conductive pillar of Example 1 by using the IMS method, and the concave shape of the sintered body. Bumps were provided along. Specifically, the molten solder was directly injected and supplied from the injection head (reservoir) holding the molten solder to the opening portion (FIG. 8 (A)). SAC305 was used as the solder alloy. As a result, a second bonding layer (bump) made of a solder alloy was produced. The obtained second bonding layer had a raised shape like a convex curved surface. Then, the resist layer was removed to obtain the conductive pillar of Example 2 (FIG. 8 (B)).
  • SAC305 molten solder
  • the conductive pillar of Example 6 is provided on an Al electrode pad on a base material via a Cu thin film (first bonding layer) having a thickness of 250 nm, and the side surface of the sintered body is covered with the Cu thin film.
  • the height of the pillars was about 15 to 20 ⁇ m
  • the intermetallic compound layer was about 1 to 5 ⁇ m
  • the second bonding layer was about 5 to 15 ⁇ m.
  • a Cu thin film is formed on the surface of a substrate on which a resist layer having an opening is formed, and the exposed substrate is exposed after the step of removing the resist layer. Since there is no Cu thin film on No. 11 and it is not necessary to provide an etching step for removing the Cu thin film, undercut does not occur.
  • the diameter of the conductive pillar is almost the same as the diameter of the opening pattern.
  • Example 7 ⁇ Preparation of joint structure> Next, a base material in which a second bonding layer (bump) made of a solder alloy is formed on the conductive pillar of Example 6 made of a sintered body, and a Si substrate (bonded) having an electrode made of copper on the surface.
  • the members were placed facing each other and laminated. Specifically, the electrode of the member to be joined is arranged with the surface provided with the electrode of the member to be joined facing upward, and the surface on which the second bonding layer of the base material is formed is arranged facing downward. And the second bonding layer of the base material were overlapped (FIG. 8 (C)).
  • the height of the conductive pillar after chip assembly was 20 ⁇ m.
  • Example 7 (Electrical resistance measurement and insulation reliability test) Regarding the bonded structure of Example 7 in which the base material and the member to be bonded were bonded by the conductive pillar of Example 6, the electrical resistance measurement and the insulation reliability test of the conductive pillar were carried out by the evaluation method described later.
  • Example 8 ⁇ Preparation of joint structure> After that, the sealing resin is filled in the region where the bonding structure is not arranged between the base material and the member to be bonded by injecting an underfill agent made of an epoxy resin to obtain the bonding structure of Example 8. (FIGS. 9 (A) and 9 (B)).
  • a bonding structure having a sintered body 12 of conductive pillars and a bonding layer 22 provided along the concave shape of the sintered body 12 was formed between the base material 11 and the member 21 to be bonded. (FIGS. 9 (A) and 9 (B)).
  • High temperature storage test (HTS test) A high temperature storage test (HTS test) was carried out on the joint structure of Example 8 provided with the conductive pillars of Example 6 by the evaluation method described later.
  • the resist was exposed and developed to form a plurality of aperture patterns so that openings were provided on the Al electrodes.
  • the shape of the opening pattern of the resist layer consists of a cylindrical shape with a diameter of 30 to 75 ⁇ m on the top and bottom surfaces, and a square prismatic recess with a side of 30 to 75 ⁇ m on the top and bottom surfaces, and the depth of the opening is It was 30 ⁇ m.
  • the aspect ratio (depth: diameter) of the cylindrical opening was designed to be 1.0: 1.0 to 2.5.
  • the molten solder was injected from the reservoir holding the molten solder, and the molten solder was directly supplied to the opening.
  • the solder alloy SAC305 was used.
  • a conductive pillar made of only a solder alloy was produced.
  • the solidified solder alloy showed a shape in which its head was raised in a convex curved surface shape due to the difference in surface energy from the resist layer.
  • the resist layer was removed, and then the exposed Cu thin film was etched and removed by immersing it in a copper etching agent (WLC-C2 manufactured by Ryoe Chemical Co., Ltd.) to obtain the conductive pillar of Comparative Example 1.
  • a Cu thin film is formed on the entire surface of the base material, and a resist pattern is further formed on the Cu thin film.
  • a Cu thin film is formed below the solder alloy. Therefore, when the Cu thin film is etched after the resist strip, the solder alloy does not elute, but the Cu thin film under the conductive pillar also elutes together with the exposed Cu thin film, resulting in undercut.
  • the base material and the member to be joined were heated in a laminated state to melt the solder alloy, and the base material and the member to be joined were joined to form the bonding structure of Comparative Example 2.
  • the height of the conductive pillar after chip assembly was 15 ⁇ m.
  • High temperature storage test (HTS test) A high temperature storage test (HTS test) was carried out on the bonded structure of Comparative Example 3 provided with the conductive pillars of Comparative Example 1 by the evaluation method described later.
  • the shape of the opening pattern of the resist layer consists of a cylindrical shape with a diameter of 30 to 75 ⁇ m on the top and bottom surfaces, and a square prismatic recess with a side of 30 to 75 ⁇ m on the top and bottom surfaces, and the depth of the opening is It was 30 ⁇ m.
  • the aspect ratio (depth: diameter) of the cylindrical opening was designed to be 1.0: 1.0 to 2.5.
  • the prepared electrode base material was immersed in 5 wt% sulfuric acid to perform a pretreatment for removing the oxide film.
  • a copper plating solution consisting of 65 g / L of copper sulfate pentahydrate, 170 g / L of sulfuric acid, and 70 mg / L of sodium chloride was prepared.
  • the pretreated electrode base material was immersed in a copper plating solution and polarized.
  • the exposed cathode electrode surface of the pattern opening of the resist layer was plated with copper to prepare a conductive pillar made of copper plating.
  • the molten solder was injected from the reservoir holding the molten solder, and the molten solder was directly supplied to the opening.
  • solder alloy SAC305 was used. As a result, a conductive pillar made of only a solder alloy was produced.
  • the solidified solder alloy showed a shape in which its head was raised in a convex curved surface shape due to the difference in surface energy from the resist layer.
  • the resist layer is removed by etching, then the exposed Cu thin film is removed by etching by immersing it in a copper etching agent (WLC-C2 manufactured by Ryoe Chemical Co., Ltd.), and finally, the exposed Ti thin film is sputtered Ti etching for wafer bumps. Etching was removed by immersing in an agent (WLC-T manufactured by Ryoe Chemical Co., Ltd.) for 20 seconds to obtain a conductive pillar of Comparative Example 4.
  • the conductive pillar of Comparative Example 4 used for evaluation was a cylinder having a diameter of 75 ⁇ m and a pillar height of 20 ⁇ m. However, the diameter of the layer of the Ti thin film portion was small and etched, resulting in undercut.
  • the conductive pillars are formed by the plating method as in Comparative Example 4, it is necessary to form a Cu thin film to be the cathode electrode surface on the entire surface of the base material. Therefore, undercut occurs in the etching after the resist strip.
  • the base material and the member to be joined were heated in a laminated state to melt the joining layer, and the base material and the member to be joined were joined to form the joining structure of Comparative Example 5.
  • the height of the conductive pillar after chip assembly was 20 ⁇ m.
  • High temperature storage test (HTS test) A high temperature storage test (HTS test) was carried out on the bonded structure of Comparative Example 6 provided with the conductive pillars of Comparative Example 4 by the evaluation method described later.
  • Table 1 shows the measurement results of the average value and standard deviation.
  • the bonding strength (share strength) between the conductive pillars and bumps of Examples 2 and 6 is the bonding strength (share strength) between the conductive pillars and bumps of Comparative Example 1 composed of only a solder alloy. It was superior to the above, and was as excellent as the joint strength (share strength) between the conductive pillar and the bump of Comparative Example 4 composed of only copper plating.
  • the resistance value of the conductive pillar was obtained.
  • the resistance of the connection circuit part other than the conductive pillar is a minute resistance and can be ignored.
  • Table 2 shows the measurement results of the average value and standard deviation of the 16 measured values. As shown in Table 2, the bonding structures of Examples 3 and 7 showed good conductivity equivalent to the bonding structure of Comparative Example 2 and the bonding structure of Comparative Example 5.
  • Each joint structure is installed in an accelerated life test device (manufactured by HIRAYAMA, trade name: PL-422R8, condition: 130 ° C./85% RH / 100 hours, 3.7 V applied), and a test piece for insulation reliability test.
  • HIRAYAMA trade name: PL-422R8, condition: 130 ° C./85% RH / 100 hours, 3.7 V applied
  • a test piece for insulation reliability test Got After polishing the test piece, an image of a cross section of the connection portion was captured and evaluated using a metallurgical microscope (BX60, manufactured by OLYMPUS Corporation).
  • the image processing software Adobe Photoshop, the corroded portion was identified by color tone correction and two-gradation, and the proportion of the corroded portion was calculated from the histogram.
  • the semiconductor adhesive portion between the two bumps of the connection portion was set to 100%, and the discolored portion within that range was calculated by the same method as described above.
  • Temperature cycle test (DTC test)
  • 10 test pieces of cylindrical conductive pillars having a top and bottom diameters of 40 ⁇ m were collected. , These were subjected to a temperature cycle test (DTC test). After the moisture absorption reflow (Moisture Sensitivity Level: MSL), a temperature cycle (Deep Thermal Circle: DTC) test was performed.
  • MSL moisture absorption reflow
  • DTC Deep Thermal Circle
  • High temperature storage test (HTS test)
  • the HTS test High Temperature Story Test
  • Each test piece was exposed to a high temperature environment at a temperature of 150 ° C. for 1000 hours using a high temperature incubator. The test piece was taken out every 500 hours and the resistance value was measured.
  • the electric resistance value of the wiring in which 80 or 82 conductive pillars were connected in series was measured by the 4-terminal method, and the rate of change ( ⁇ R) of the electric resistance value was determined.
  • ⁇ R rate of change
  • Table 3 the joining structure of Example 4 joined by the conductive pillars of Example 2, the joining structure of Example 8 joined by the conductive pillars of Example 6, and the conductive pillars of Comparative Example 1.
  • the bonding structure of Comparative Example 3 bonded by the above and the bonding structure of Comparative Example 6 bonded by the conductive pillar of Comparative Example 4 were all within the range of ⁇ R ⁇ 2%, which were good.
  • the conductive pillars of the examples have excellent bonding strength (share strength) with the bumps, so that the bonding structure of the examples is higher between the base material and the member to be bonded. It can be joined with the joining strength.
  • the bonding structure of the examples showed good evaluation results in all of the electrical resistance, insulation reliability, temperature cycle test, and high temperature storage test.
  • Electrode pad 16: Resist layer, 16a: Opening, 17: Cu thin film, 17a: Cu thin film on the upper part of the resist layer, 17b: Cu thin film on the side surface of the sintered body (Cu thin film on the side surface of the opening of the resist layer), 17c: First bonding layer (Cu on the electrode pad). Thin film), 17d: Cu thin film under the resist layer, 20: bonded structure, 21: bonded member, 22: second bonded layer, 22b: injection head, 23: electrode, 25: intermetallic compound layer, 26: Encapsulating resin.

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  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Powder Metallurgy (AREA)
  • Conductive Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Procédé de fabrication d'un pilier conducteur pouvant lier un substrat et un élément à lier par l'intermédiaire d'une couche de liaison avec une force de liaison élevée sans utilisation d'un procédé d'électroplacage, et procédé de fabrication d'une structure liée l'utilisant. Un procédé de fabrication d'un pilier conducteur 1 comprend, dans un ordre à mentionner, une étape de formation d'une couche de réserve 16 sur un substrat 11 sur lequel est formé un plot d'électrode 13, la couche de réserve 16 présentant une ouverture 16a sur le plot d'électrode 13, une étape de pulvérisation ou de dépôt de Cu sur une surface du substrat 11, sur laquelle la couche de réserve 16 ayant l'ouverture 16a est formée, pour former un film mince de Cu 17, une étape de remplissage de l'ouverture 16a avec une pâte de particules fines de cuivre 12c, et une étape de chauffage du substrat 11 rempli de la pâte de particules fines de cuivre 12c pour fritter la pâte de particules fines de cuivre 12c.
PCT/JP2020/047075 2020-01-17 2020-12-17 Pilier conducteur et son procédé de fabrication, et procédé de fabrication de structure liée WO2021145129A1 (fr)

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US17/791,652 US20230041521A1 (en) 2020-01-17 2020-12-17 Conductive pillar, method for manufacturing the same, and method for manufacturing bonded structure
JP2021549079A JP7107448B2 (ja) 2020-01-17 2020-12-17 導電性ピラー及びその製造方法並びに接合構造の製造方法
KR1020227023782A KR20220128352A (ko) 2020-01-17 2020-12-17 도전성 필러 및 그 제조 방법 그리고 접합 구조의 제조 방법

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US20180061796A1 (en) * 2016-09-01 2018-03-01 International Business Machines Corporation Method of forming a solder bump structure
US20180076163A1 (en) * 2016-09-14 2018-03-15 International Business Machines Corporation Method of forming solder bumps

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US8592995B2 (en) 2009-07-02 2013-11-26 Taiwan Semiconductor Manufacturing Company, Ltd. Method and structure for adhesion of intermetallic compound (IMC) on Cu pillar bump
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JPH08222840A (ja) * 1995-02-15 1996-08-30 Sumitomo Metal Ind Ltd 電極パッド付き回路基板およびその製造方法
JP2010109380A (ja) * 2009-12-25 2010-05-13 Toshiba Corp 微粒子膜形成装置・形成方法、ならびに半導体装置およびその製造方法
JP2014143305A (ja) * 2013-01-24 2014-08-07 Nippon Telegr & Teleph Corp <Ntt> 半導体装置の実装構造および半導体装置の製造方法
JP2016115846A (ja) * 2014-12-16 2016-06-23 三菱マテリアル株式会社 ピラー形成用ペースト、ピラーの製造方法、バンプ構造体の製造方法、ピラー、及びバンプ構造体
US20180061796A1 (en) * 2016-09-01 2018-03-01 International Business Machines Corporation Method of forming a solder bump structure
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116153860A (zh) * 2023-04-10 2023-05-23 之江实验室 晶圆级铜铜凸点互连结构及其键合方法
CN116153860B (zh) * 2023-04-10 2023-07-18 之江实验室 晶圆级铜铜凸点互连结构及其键合方法

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US20230041521A1 (en) 2023-02-09

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